Powder materials containing copper ions supported on ZSM-5 (Cu-Zeolite Socony Mobil-5) and SSZ-13 (Cu-Standard Oil synthesised zeolite-13), and predominantly CuO nanoparticles on amorphous SiO ${}_2$ were synthesised, characterised, wash-coated onto ceramic monoliths and, for the first time, compared as catalysts for direct conversion of methane to methanol (DCMM) at ambient pressure (1 atm) using O ${}_2$ , N ${}_2$ O and NO as oxidants. Methanol production was monitored and quantified using Fourier transform infrared spectroscopy. Methanol is formed over all monolith samples, though the formation is considerably higher for the copper-exchanged zeolites. Hence, copper ions are the main active sites for DCMM. The minor amount of methanol produced over the Cu/SiO ${}_2$ sample, however, suggests that zeolites are not the sole substrate that can host those active copper sites but also silica. Further, we present the first ambient pressure in situ infrared spectroscopic measurements revealing the formation and consumption of surface methoxy species, which are considered to be key intermediates in the DCMM reaction.

Oxygen activation is a key step in the selective catalytic reduction of nitrogen oxides with ammonia (NH₃‐SCR) over Cu‐chabazite. We present direct measurements of oxygen adsorption at low temperatures over [NH₃−Cu−NH₃]⁺ complexes and framework‐bound Cu⁺ species in Cu‐chabazite with Si/Al=14 using isothermal microcalorimetry combined with mass spectrometry. The enthalpy change for O₂ adsorption over [NH₃−Cu−NH₃]⁺ complexes at 200 °C is determined to be −79 kJ/mol. By fitting a Langmuir isotherm, the corresponding entropy change is determined to be −142 J/(mol*K) at 10 % O₂. The results show that O₂ adsorption at low temperatures over [NH₃−Cu−NH₃]⁺ complexes is more facile than on framework‐bound Cu⁺ species. The experimental results are in agreement with density functional theory calculations showing a lower barrier for O₂ activation over the [NH₃−Cu−NH₃]⁺ complexes as compared to the framework‐bound Cu⁺ species.

Study of desorption products from Cu-zeolites (MFI and CHA) during methanol-TPD using a chemical flow reactor with a gas phase FTIR spectrometer.

Boron silicate (BS) with a chabazite framework structure was synthesised using a direct route and rigorously characterized before it was ion-exchanged with copper to form Cu-BS. Employing in situ infrared spectroscopy, we show that Cu-BS is capable of oxidising methane to methoxy species and methanol interacts with the boron sites without deprotonation.

The Front Cover shows an oxygen molecule activated on a pair of Cu‐ammonia complexes in a chabazite cage, which is an important reaction intermediate in ammonia‐assisted NO_x reduction over Cu‐chabazite. In their Full Paper, X. Wang, L. Chen et al. investigate the heat generated through the oxygen activation process over Cu‐ammonia complex pairs in chabazite. The authors present measurements and first principle calculations of the adsorption enthalpy and entropy. Their results show that oxygen activation is promoted by the Cu‐ammonia complexes thanks to the mobility of these Cu species in chabazite. More information can be found in the Full Paper by X. Wang, L. Chen et al.